Die Iodierung von <i>cyclo</i>‐E<sub>5</sub>‐Komplexen (E=P, As)

Recently there has been great interest in the reactivity of transition‐metal (TM) centers towards white phosphorus (P4). This has ultimately been motivated by a desire to find TM‐mediated alternatives to the current industrial routes used to transform P4 into myriad useful P‐containing products, which are typically indirect, wasteful, and highly hazardous. Such a TM‐mediated process can be divided into two steps: activation of P4 to generate a polyphosphorus complex TM‐Pn, and subsequent functionalization of this complex to release the desired phosphorus‐containing product. The former step has by now become well established, allowing the isolation of many different TM‐Pn products. In contrast, productive functionalization of these complexes has proven extremely challenging and has been achieved only in a relative handful of cases. In this review we provide a comprehensive summary of successful TM‐Pn functionalization reactions, where TM‐Pn must be accessible by reaction of a TM precursor with P4. We hope that this will provide a useful resource for continuing efforts that are working towards this highly challenging goal of modern synthetic chemistry.

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Transition‐Metal‐Mediated Functionalization of White Phosphorus

Hoidn

Scott

Wolf

2020

Chemistry A European J

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Versatile Coordination of Ag^I and Cu^I Ions towards cyclo‐As₅ Ligands

Moussa

Fleischmann

Baláȥs

et al. 2021

Chemistry A European J

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The reactions of the cyclo‐As5 complex [Cp*Fe(η5‐As5)] (B) with the AgI and CuI salts of the weakly coordinating anion (WCA) [FAl{OC6F10(C6F5)}3]− ([FAl]−) are studied. These reactions allow the synthesis of the mononuclear complexes [M(η5 : η2‐B)2][FAl] (M=Ag (1), Cu (2)) when a ratio of B/M(FAl) 2 : 1 is used. Compound 1 shows an unusual disorder of the central AgI cation between two π‐coordinating cyclo‐As5 ligands, which is absent in 2 pointing to a weak interaction of the Ag center towards the cyclo‐As5 ligands in B. When the ratio of B/Ag(FAl) is changed to 3 : 1 or 1 : 1, the respective coordination compounds [Ag(η2‐B)3][FAl] (3) and [Ag2(η2 : η2‐B)2][FAl]2 (4) are accessible. The coordination modes of the cyclo‐As5 units in 1, 3 and 4 are all different, reflecting the adaptive coordination behavior of B towards AgI ions. The optimized geometries in the gas phase of 1–4 are determined by DFT calculations to support the bonding situation observed in their solid‐state structures.

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Halogenation and Nucleophilic Quenching: Two Routes to E−X Bond Formation in Cobalt Triple‐Decker Complexes (E=As, P; X=F, Cl, Br, I)

Garbagnati

Piesch

Seidl

et al. 2022

Chemistry A European J

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The oxidation of [(Cp’’’Co)2(μ,η2 : η2‐E2)2] (E=As (1), P (2); Cp’’’=1,2,4‐tri(tert‐butyl)cyclopentadienyl) with halogens or halogen sources (I2, PBr5, PCl5) was investigated. For the arsenic derivative, the ionic compounds [(Cp’’’Co)2(μ,η4 : η4−As4X)][Y] (X=I, Y=[As6I8]0.5 (3 a), Y=[Co2Cl6‐nIn]0.5 (n=0, 2, 4; 3 b); X=Br, Y=[Co2Br6]0.5 (4); X=Cl, Y=[Co2Cl6]0.5 (5)) were isolated. The oxidation of the phosphorus analogue 2 with bromine and chlorine sources yielded the ionic complexes [(Cp’’’Co)2(μ‐PBr2)2(μ‐Br)][Co2Br6]0.5 (6 a), [(Cp’’’Co)2(μ‐PCl2)2(μ‐Cl)][Co2Cl6]0.5 (6 b) and the neutral species [(Cp’’’Co)2(μ‐PCl2)(μ‐PCl)(μ,η1 : η1‐P2Cl3] (7), respectively. As an alternative approach, quenching of the dications [(Cp’’’Co)2(μ,η4 : η4‐E4)][TEF]2 (TEF=[Al{OC(CF3)3}4]−, E=As (8), P (9)) with KI yielded [(Cp’’’Co)2(μ,η4 : η4‐As4I)][I] (10), representing the homologue of 3, and the neutral complex [(Cp’’’Co)(Cp’’’CoI2)(μ,η4 : η1‐P4)] (11), respectively. The use of [(CH3)4N]F instead of KI leads to the formation of [(Cp’’’Co)2(μ‐PF2)(μ,η2 : η1 : η1‐P3F2)] (12) and 2, thereby revealing synthetic access to polyphosphorus compounds bearing P−F groups and avoiding the use of very strong fluorinating reagents, such as XeF2, that are difficult to control.

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Die Iodierung von cyclo‐E₅‐Komplexen (E=P, As)

Cited by 4 publications

References 47 publications

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Versatile Coordination of Ag^I and Cu^I Ions towards cyclo‐As₅ Ligands

Halogenation and Nucleophilic Quenching: Two Routes to E−X Bond Formation in Cobalt Triple‐Decker Complexes (E=As, P; X=F, Cl, Br, I)

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Die Iodierung von cyclo‐E5‐Komplexen (E=P, As)

Cited by 4 publications

References 47 publications

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Versatile Coordination of AgI and CuI Ions towards cyclo‐As5 Ligands

Halogenation and Nucleophilic Quenching: Two Routes to E−X Bond Formation in Cobalt Triple‐Decker Complexes (E=As, P; X=F, Cl, Br, I)

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Die Iodierung von cyclo‐E₅‐Komplexen (E=P, As)

Versatile Coordination of Ag^I and Cu^I Ions towards cyclo‐As₅ Ligands